Physical Sciences and Mathematics Commons^™

Part A: Some Reactions Of Norbornene Oxide: Part B: Arylnorbornene Oxides, Thomas J. Gerteisen

Doctoral Dissertations

Part A: In this thesis research on the action of Grignard reagents with with norbornene oxide has been initiated and found to be of possible synthetic utility.

Part B: The structure of the product of the acid catalyzed dehydration of 2-p-anisylnorbornane-2, 3-cis-exo-diol in hydrochloric acid-tetrahy-drofuran has been reassigned. It was discovered, on the basis of further data, that the structure of the high melting solid was that of the dimer of the epoxide, a p-dioxane, rather than the epoxide itself. This change was proposed for many reasons. A near total nmr analysis of the compound …

Cell-Free Amino Acid-Incorporating Systems From Mesofhilic And Thermophilic Species Of The Genus Bacillus, Nisson Schechter

Dissertations

No abstract provided.

The Reaction Of Ethylenediamine With Tetradentate Cobalt(Iii) Complexes, Laura H. C. Huang

Masters Theses

No abstract provided.

Cobalt(Iii) Complexes With 1,2-Propanediaminediacetic Acid, Paul John Magnell

Masters Theses

Introduction

Aminocarboxylic acid cobalt(III) complexes have been of interest to inorganic chemists since 1909 when Ley and Winkler isolated violet and rose colored geometric isomers of tris amino acid complexes of glycine and alanine.¹ More recently, considerable interest has been shown in the study of the stereochemistry and optical activity arising from configurational and vicinal interactions of these complexes. Nuclear magnetic resonance of the methylene protons on the carboxylate portion of the coordinated ligand has also been studied.

Of immediate interest to this study is the stereo-chemistry of complexes containing flexible tetradentate ligands. A tetradentate ligand may be constructed …

Synthesis And Structure Proof Of Cis-6,6-Dichloro-2-Diphenylmethylene- Bicyclo [3.2.0] Hept-3-Ene-7-One And Cis-2,2- Dichloro- 1,2,2a,7a-Tetrahydro- 7-Diphenylmethylene-Cyclobut (A) Inden-1-0ne, William Douglas Barta

Masters Theses

Introduction

The purpose of this research endeavor was to determine the structures of the adducts of dichloroketene with diphenylfulvene and benzodiphenylfulvene. Structure elucidation was attempted by chemical degradation and nmr analysis.

The structures of the adducts of dichloroketene with cyclopentadiene^1,2 and indene^3,4 have been determined by previous workers. The influence of the exocyclic double bond on the mode of cycloaddition is unknown.

Liquid Scintillators. The Photooxidation Of 2,5-Diphenyloxazole, Margaret E. Ackerman

Chemistry and Chemical Biology ETDs

Mackay had found that prolonged ultraviolet irradiation of solutions of 2,5-diphenyloxazole (PPO) (1) in toluene resulted in the formation of an insoluble crystalline product 2 which accumulated above the meniscus; the formation of 2 was dependent upon the presence of dissolved oxygen and water in the solutions. The Compound 2 was not a simple degradation product of PPO (1); elemental analysis was compatible with the empirical formula C22H17O5N and the thermal decomposition of 2 gave equal molar amounts of carbon monoxide, benzoic acid, and dibenzamide. The study described in this dissertation was initiated to establish the structure of 2 and …

The Design, Construction, And Application Of A Multibeam Fiber Optics Photometric Titrator, Marlin George Bensinger

Masters Theses

No abstract provided.

The Synthesis And Photolysis Of Kreysiginone And The Syntheses And Antibacterial Activity Of 1-Vinyl-3,4-Dihydroisoquinoline Methiodides, Bruce L. Jensen

Dissertations

No abstract provided.

Part I. The Stereochemistry Of Carbanions Formed By Base Catalyzed Decomposition Of Azoacetates Part Ii. Anomalous Decarbonylation Of 4 –Substituted Carboxylic Acids With Thionyl Chloride, Tai-Shun Lin

Dissertations

Introduction

Although the stereochemical capabilities of carbonium ions have been extensively investigated, the stereochemical fate of carbanions has been subjected relatively little to systematic scrutiny. The fact that only a limited number of clean-cut sources of carbanions are available has added difficulty to such investigations.

The stereochemical capabilities of carbanions has been extensively and thoroughly examined in recent years by Cram and coworkers. However, the carbanion carbon developed in the reactions employed was bonded in every case to an unsaturated (usually aromatic) group. No fully aliphatic carbanion has been subjected to such a stereochemical study.

The reaction of lead tetraacetate …

The Reaction Of Acetaldehyde With Some Cobalt (Iii) Complexes Containing Coordinated Glycine, James C. Dabrowiak

Dissertations

No abstract provided.

The Chemistry Of Dehydronaphthalene, Richard Harold Hales

Theses and Dissertations

The reaction of monohalonaphthalenes with potassium t-butoxide in a t-butyl alcohol-dimethyl sulfoxide (DMSO) mixture has been studied. The 1-bromonaphthalene reaction was extensively studied. Fifteen identifiable products were observed and conditions were found where the desired products, 1- and 2-t-butyl naphthyl ethers (V and VI) were formed in maximum yield, and their decomposition products, 1- and 2-naphthol (XIV and XV), were formed in minimum yield. The mole percent ratio of 1-substituted products (V and XIV) to 2-substituted products (VI and XV) was found under standardized conditions to be 0.35 ± 0.03 in every case when the halogen was I, Br and …

The Effects Of Various Treatments On Thiamin Diphosphate And Total Thiamin Levels Of Rat Tissues, Dong Hwa Park

Theses and Dissertations

Tissue thiamin diphosphate was assayed enzymatically utilizing purified brewer's yeast apotransketolase. With this assay ten uumoles of thiamin diphosphate could be detected. Total thiamin was fluorometrically measured. For one to three days rats were placed under conditions of stress, consisting of loud noise treatment, emotional stress, deprivation of paradoxical sleep, and swimming to exhaustion, respectively. The body weight was markedly decreased at the end of the respective experimental periods except with the loud noise treated group, compared with the corresponding controls. Following two to three such consecutive treatments, the adrenal weight also showed a significant increase. Thiamin diphosphate and total …

A Spectroscopic Investigation Of Electron Transfer Transitions In Osmium (Ii) Complexes., Brian J. Pankuch

Chemistry and Chemical Biology ETDs

Osmium (II) complexes containing organic coordinating ligands 2.2'-bipyridine, 1.10-phenanthroline, 2.2' .2"­terpyridine were studied spectroscopically. Syntheses were carried out by published methods, and each complex was checked by chemical analysis and thin layer chromatography. The complexes were shown to be d6 strong field systems by magnetic susceptibility measurements performed at room temperature in air.

Room temperature absorption spectra in the visible and near-ultraviolet were measured in solvents of different polarities (H₂O, MeOH, CH₃CN, DMF, CHCl₃) and solvent shifts of the band maxima of 0.3 to 3 kK were found. Low temperature (approximately 82-90°K) absorption spectra …

Quantitative Spark-Source Mass Spectrometric Techniques For The Simultaneous Determination Of The Lanthanide And Actinide Elements In Microgram And Sub-Microgram Transuranium Samples, Joel Avery Carter

Doctoral Dissertations

The work presented encompasses techniques developed for the analysis of certain rare earth and actinide elements in solutions containing highly radioactive transuranium elements. Advantage was taken of the high inherent resolution and sensitivity of the rf spark-source mass spectrometer in the development of qualitative and quantitative procedures where an analysis can be made on a total sample of <1 to 10 μg. Parameters for the Associated Electrical Industries' MS-702 spark-source mass spectrometer were adjusted so that mass-to-charge ratios in the range of 10 to 310 could be subjected to qualitative analysis. For quantitative assessment of impurities in a transuranium solution, relative sensitivity factors were established with respect to erbium, the internal standard, for rare earth elements and for thorium, uranium, neptunium, americium, curium, berkelium, and californium.

A special glove box was designed, fabricated, and used on the source end of the mass spectrometer so that samples of the transuranium elements could be run safely. Transuranium element with α-emitting radioactivity up to 10¹⁰ dpm were processed through the …

Stability Of 1-Substituted Adenines, Walter Frederick Floser

Honors Theses

1-β-Hydroxyethyladenine was prepared by the reaction of ethylene chlorohydrin with adenine at 76° C. It was separated from the reaction mixture by use of a Dowex 50W-X8 cation exchange chromatography column and a linear gradient elution system. I was placed in aqueous alkaline solution for two weeks and checked at different intervals to determine its stability. I was also refluxed in an aqueous alkaline solution for 70 min. and its stability was checked. I proved to be stable under all conditions.

Photochemical Reduction Of Benzophenone By 2-Butyne-L, 4-Diol And Photochemical Solvolysis Reactions Of Beta-Phenethyl Compounds, Kenneth Lawrence Gordon

Honors Theses

The irradiation of a dioxane solution of benzophenone in the presence of 2-butyne-1, 4-diol leads to reduction of the ketone rather than addition across the triple bond of the alkyne. However, great difficulty was encountered in identifying the product due to the formation of an organic complex involving benzopinacol and the dioxane. Nuclear magnetic resonance and ultraviolet spectral data confirm the presence of the complex. An attempt was made to induce a known ground state reaction by photochemical means. This ground state reaction is known to proceed through an ethylene phenonium ion intermediate. Both β-phenethyl bromide and β-phenethyltrimethylammonium tetrafluoroborate were …

Determination Of Ring Orientation In Diphenylmethane And Derivatives, Patrick Michael Comi

Honors Theses

Nuclear Magnetic Resonance Spectrometry, like infrared, visible, and ultraviolet spectrometry is a form of absorption spectrometry. Certain nuclei can absorb electromagnetic radiation in the radiofrequency range. These nuclei are able to absorb this energy because they “spin” about their center axis generating a dipole along it. Protons are among those nuclei that absorb radiofrequency energies. If a proton is placed in a magnetic field its dipole can be in one of two possible orientations. It can be in a low energy state aligned with the field, or a high energy state, a spinning proton will process about an axis at …

Synthesis Of N-Methyl-N-Phenylaminomethyltrimethylsilane And N, N-Dimethylanilinomethyltrimethylsilyl Iodide, Mark Stuart Lichtenstein

Honors Theses

N-Methyl-N-Phenylaminomethyltrimethylsilane (I) has been prepared by heating an ethereal solution of lithium N-Methyl-anilide and chloromethyltrimethylsilane in a sealed flask for two days at 110°. The peak ratios in the NMR spectrum of the product did not correspond to these expected for I but suggested a different product, N-Methyl-N-Trimethylsilylaniline (II). Elemental analysis favored II although it could also be interpreted to support I. The spectra of derivatives, and the substance’s stability to hydrochloric acid were characteristic of I. Tentative identification of ethylene as a by-product, and a small degree of reaction with hydrochloric acid support the presence of II, but only …

Halogenated Helicenes, Richard Wilbert Heiden

Honors Theses

Attempts at synthesizing certain halohelicenes for studies in the following areas are described: 1) the testing of a new method of resolving 2) electron spin resonance (ESR). Since the purpose of the study was twofold, the decision to synthesize monochloro derivatives of hexahelicene was based on the time element and the comparative ease in which these particular compounds were thought to have been brought about (i.e. in direct comparison to polyhalo and higher order helicenes). In addition to the traditional historical, theoretical, and experimental sections, an appendix contained a few suggestions relative to helicene research is included.

Calculations Of Total Energies For Neon Atom, Argon Atom And Neon Ion, Joseph Patrick Minehan

Honors Theses

This work shows that is is very difficult to guess the proper configuration of the spheres for most atoms. This is clearly shown in the argon calculations, where Bent suggested a configuration that would have lowest energy, but it turned out to have the highest energy of those calculated. This shows the need to have a method to give the configuration of the lowest energy that depends very little on human insight.

Synthetic Approaches To Tris (1-B, 8-B'-Naphthyl) Diboron, William Karl Goerich

Honors Theses

The purpose of this project was the synthesis of tris(l-B, 8-B'­naphthyl)diboron. The synthesis route attempted was the preparation of 1,8-dibromonaphthalene from 1,8-diaminonaphthalene by tetrazotization followed by a Sandmeyer reaction, treatment of the dibromo compound with n-butyllithium to give 1,8-dilithionaphthalene and subsequent addition of boron trifluoride to give the product.

The Enzymatic Oxidation Of Aldehydes By Xanthine Oxidase, Duane Beal Gregory

All Master's Theses

As early as sixty years ago, the existence of an enzyme from mammalian tissues which catalyzed the oxidation of xanthine and hypoxanthine was recognized. The name given the enzyme was derived from its earliest recognized action, hence xanthine oxidase. Although little is known about the biological functions of the enzyme, the high affinity shown for xanthine and hypoxanthine may indicate that these are the most significant substrates biologically.

Preparation Of New Amino-, Thio-, And Sulfonyladamantane Derivatives, Joseph Craig Argyle

Theses and Dissertations

Various synthetic schemes were used to prepare a number of new amino-thio- and sulfonyladamantane compounds. By a nucleophilic substitution on 1-bromoadamantane, 1-(p-nitrophenylthio)adamantane was prepared from p-nitrothiophenol; the amino- and sulfonyl- derivatives of this compound were also prepared. Silver tosylate was used to generate the 1-adamantyl carbonium ion from 1-bromoadamantane in a synthetically useful procedure for preparing 1-adamantylamides from nitriles. Three 1-(1-adamantylcarbinyl)-2,5-dialkylpyrroles were prepared by Knorr-Paal reactions and reduced to the corresponding pyrrolidines. Thio- and aminomethyl 1-adamantyl ketones were prepared from methyl and bromomethyl 1-adamantyl ketones, respectively. Aliphatic and aromatic oxiranes were reacted with 1-aminoadamantane in a bomb at elevated temperatures …

The Reactivity And Selectivity Of The Reaction Of Sulfur Trioxide And Bromobenzene, Sullivan E. Blau

Theses and Dissertations

The sulfonation of bromobenzene with sulfur trioxide in liquid sulfur dioxide at -12 to -13° C. was studied to determine its relative reactivity. The relative rate constant ratio, kbenzene/kbromobenzene, was found to be 28.6 in a competitive reaction between benzene and bromobenzene. The isomer distribution was found to be 0.15 ± 0.02% for the meta, 0.91 ± 0.04% for the ortho and 98.93 ± 0.14% for the para isomers. The partial rate factors were calculated to be pf= 0.208, of= 0.0096 and mf = 0.00018. The relative rate data exhibited a distinctive behaviour previously noted in related systems, possibly due …

The Synthesis And Properties Of New Potentially Chemotheraputic [Sic] Pteridine Derivatives, Walter Wesley Parish

Theses and Dissertations

A new general synthetic method for the preparation of 6-thiopteridines has been developed. The method involves the addition of thiols to intermediate pyrimidine nitrones formed in situ by the reaction of 4-amino-5-nitrosopyrimidines with pyridinium-activated acetonitriles, acetates, acetophenones, and other methylketones. Ca. forty new pteridines were prepared by this method. The preparation of six new 6-pteridinyl ketones, two new 6- pteridinyl ketone thiosemicarbazones, and two new 6-sulfonylpteridines and their 4-acetamido derivatives is also reported. 4-Acetamido-2- amino-7-phenylpteridine 5-oxide was prepared by the reaction of 2- amino-4,6-diacetamido-5-nitrosopyrimidine with either phenylsulfonyl-acetophenone or phenacylpyridinium bromide. Evidence relating to the structure of the acylated 4-amino-5- nitrosopyrimidines …

High Pressure Spectral Chemistry Of Selected Organic Compounds, Frank William Linsley

Theses and Dissertations

The series of compounds indicated by the formular C_6H_5-(CH=CH)n-C_6H_5 change in color from white (colorless) to yellow to orange to red to deep red as n increases from 1 to 12. Stilbene is the first compound of this series (n=1). Under pressure, exerted by a diamond anvil press, stilbene can be seen to change color from white to yellow to red as increasing pressure is applied. Similar color changes are observed for the compounds where n=2,3, and 4 when subjected to similar pressure. This study records and reports the spectra versus pressure for these compounds.

The Chemistry Of Trifluorothiolacetic Acid, Patricia Diane Weeks

Dissertations and Theses

Addition reactions of perfluorothiolacetic acid (TFTAA) with organic and inorganic substrates were studied and six new compounds containing the trifluoroacetyl group have been prepared. Two types of reactions were observed, free radical and nucleophilic addition. Under the influence of ultraviolet light, TFTAA (CF₃COSH) adds to olefins to form 1:1 adducts. The CF₃COS• radical appears to be the adding species. Three new olefin adducts were prepared: CF₃COSCFHCF₂H, CF₃COSCH₂CF₂H, and CF₃COSCH₂CFH₂. In addition, this was found to be a new way to prepare CF₃COSCH₂CH₃, which had been previously prepared by another route. Physical constants, analytical data, infrared, ultraviolet, nmr and mass spectra …

Donor Properties Of Dimethylsulfoniumcyclopentadienylide And Tetramethylenesulfoniumcyclopentadienylide In Metal Complexes ; Part Ii. The Attempted Preparation Of Boron Tricyanide, Gary Scott Barney

Theses and Dissertations

Part I.--Complexes of dimethylsulfoniumcyclopentadientylide and tetramethylenesulfoniumcyclopentadienylide with metal ions were studied in order to determine the coordination site on the ylids. Infrared spectra indicate that the ylids are coordinated through the cyclopentadienyl ring in all complexes except for the Hg(CN)2 complexes. Coordination-of the HgI2, CdI2, ZnCl2, and AgNO3 complexes is through the number one position on the ring as suggested by NMR data. Infrared and NMR data strongly indicate that the ylids in the Hg(CN)2 complexes are coordinated through sulfur. Part II.--The only method given in the chemical literature for the preparation of boron tricyanide could not be duplicated in …

A Study Of Substituent Effects In Selected Aromatic Systems By Nuclear Magnetic Resonance Spectroscopy, Carol K. Haas

Chemistry Honors Papers

This 53 page thesis builds upon previous work investigating substituent effects on nuclear magnetic resonance spectroscopy parameters.

The Photochemical Reduction Of Octacyanomolybdate(V) Ion In Aqueous Solutions, Gordon W. Gray

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The photochemical reactions occurring in aqueous solutions of octacyanomolybdate(V) ion, Mo(CN)₈^3-, during irradiation with light of 365 and 436 nm wavelengths were studied. The quantum yields and reaction products were determined for neutral, unbuffered solutions as well as solutions buffered at pH 4.0, 7.0, and 9.0.

The results of these studies showed that the Mo(CN)₈^3- ion is rapidly reduced by light to a Mo(IV) complex. In neutral or acidic media, the initial photoreduction product was found to be the red heptacyanoaquomolybdate(IV) ion, Mo(CN)₇(H₂O)^3-. Photolysis in basic solution gave the …